gem‐Difluoroallylation of Aryl Halides and Pseudo Halides with Difluoroallylboron Reagents in High Regioselectivity

We report the palladium‐catalyzed gem‐difluoroallylation of aryl halides and pseudo halides with 3,3‐difluoroallyl boronates in high yield with high regioselectivity, and we report the preparation of the 3,3‐difluoroallyl boronate reactants by a copper‐catalyzed defluorinative borylation of inexpensive gaseous 3,3,3‐trifluoropropene with bis(pinacolato)diboron. The gem‐difluoroallylation of aryl and heteroaryl bromides proceeds with low catalyst loading (0.1 mol % [Pd]) and tolerates a wide range of functional groups, including primary alcohols, secondary amines, ethers, ketones, esters, amides, aldehydes, nitriles, halides, and nitro groups. This protocol extends to aryl iodides, chlorides, and triflates, as well as substituted difluoroallyl boronates, providing a versatile synthesis of gem‐difluoroallyl arenes that we show to be valuable intermediates to a series of fluorinated building blocks.